Plant protection agents

ABSTRACT

Microbicide composition for plants, containing at least two active ingredient components in an amount producing synergistic activity, together with an appropriate filler, characterized in that  
     component I is the compound  
     2-[α-{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime, and  
     component II is a compound selected from the group  
     IIA) 5,7-dichloro-4-(4-fluorophenoxy)quinoline (“Quinoxyfen”);  
     IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine (“Cyprodinil”);  
     IIC) benzo(1,2,3)thiadiazole-7-carbothio-acid-S-methylester (“Acibenzolar-S-methyl”);  
     IID) 3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione (“Famoxadone”);  
     IIE) 8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine (“Spiroxamin”);  
     IIF) 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile (“Fludioxonil”);  
     IIG) 4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile (“Fenpiclonil”);  
     IIH) 1-methyl-cyclohexanecarboxylic acid-(2,3-dichloro-4-hydroxy-phenyl)-amide (“Fenhexamid”);  
     IIJ) 2-{2-[6-(2-cyano-phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxy-acrylic acid methyl ester (“Azoxystrobin”);  
     IIK) Methoximino-(2-o-tolyloxymethyl-phenyl)-acetic acid methyl ester (“Kresoxim-methyl”);  
     or repectively one of the salts or metal complexes of components I and II.

[0001] The present invention relates to new plant-protecting activeingredient mixtures having synergistically increased activity,containing at least two active ingredient components, and a process forthe application of such mixtures in plant protection, especially in thecontrol and prevention of disease outbreaks.

[0002] Component I is the compound

[0003]2-[α-{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylicacid-methylester-O-methyloxime, (EP-A-460,575); and

[0004] component II is a compound selected from the group

[0005] IIA) 5,7-dichloro-4-(4-fluorophenoxy)quinoline (“Quinoxyfen”),(EP-A-326,330);

[0006] IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine(“Cyprodinil”) (The Pesticide Manual, 10th. edition, 1994,109);

[0007] IIC) benzo(1,2,3)thiadiazole-7-carbothio-acid-S-methylester(“Acibenzolar-S-methyl”) (EP-A-313,512);

[0008] IID)3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione(“Famoxadone”) (EP-A-393,911);

[0009] IIE)8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine(“Spiroxamin”) (EP-A-281,842);

[0010] IIF) 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile(“Fludioxonil”) (The Pesticide Manual, 10th. edition, 1994, 326);

[0011] IIG) 4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile (“Fenpiclonil”)(The Pesticide Manual, 10th. edition, 1994, 302);

[0012] IIH) 1-methyl-cyclohexanecarboxylicacid-(2,3-dichloro-4-hydroxy-phenyl)-amide (“Fenhexamid”)(EP-A-379,438);

[0013] IIJ)2-{2-[6-(2-cyano-phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxy-acrylicacid methyl ester (“Azoxystrobin”) (EP-A-382,375);

[0014] IIK) Methoximino-(2-o-tolyloxymethyl-phenyl)-acetic acid methylester (“Kresoxim-methyl”) (EP-A-398,692); or repectively one of thesalts or metal complexes of components I and II.

[0015] It has now surprisingly been shown that the mixtures ofcomponents I and II according to the invention display not only additiveaction, but significant synergistically increased action in theprevention and control of plant diseases.

[0016] Favourable mixture ratios of the two active ingredients areI:II=20:1 to 1:20, preferably I:II=10:1 to 1:10, 6:1 to 1:6, 2:1 to 1:10and 10:1 to 1:2.

[0017] The active ingredient mixtures I+II according to the inventionhave very advantageous properties in the protection of plants againstthe outbreak of disease.

[0018] In addition, mixtures with compound IIc can activate the defencesystem, which is latent in the plant, against pathogenic microbialinfluences and can thus protect the plant by immunisation.

[0019] With the present active ingredient mixtures, the microorganismsappearing on plants or plant parts (fruits, flowers, foliage, stems,tubers, roots) of different useful plants can be stopped or destroyed,whereby plant parts growing later also remain free from suchmicroorganisms. They may also be used as dressings for the treatment ofplant propagation material, especially seeds (fruits, tubers, seedgrain) and plant cuttings (e.g. rice) to provide protection from fungalinfections, and against phytopathogenic fungi appearing in the soil. Theactive ingredient mixtures according to the invention are notable fortheir especially good plant tolerance and their environmentalacceptability.

[0020] The active ingredient mixtures according to the invention areeffective against the following classes of related phytopathogenicfungi: ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia,Mycosphaerella, Uncinula); basidiomycetes (e.g. the genus Hemileia,Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis,Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora,Alternaria, Pyricularia and in particular Pseudocercosporellaherpotrichoides); oomycetes (e.g. Phytophthora, Peronospora, Bremia,Pythium, Plasmopara).

[0021] Target crops for the indicated fields disclosed herein are,within the context of this invention, e.g. the following species ofplants: cereals (wheat, barley, rye, oats, rice, sorghum and the like);beets: (sugar beet and fodder beet); pip, stone and berry fruit:(apples, pears, plums, peaches, almonds, cherries, strawberries,raspberries and blackberries); leguminous plants: (beans, lentils, peas,soybeans); oil plants: (rape, mustard, poppy, olives, sunflowers,coconut, castor oil plant, cacao, peanut); cucumber plants (gourds,cucumbers, melons); fibre plants: (cotton, flax, hemp, jute); citrusfruits: (oranges, lemons, grapefruit, mandarins); vegetable varieties(spinach, lettuce, asparagus, cabbage varieties, carrots, onions,tomatoes, potatoes, peppers); Lauraceae: (avocado, cinnamon, camphor) orplants such as maize, tobacco, nuts, coffee, sugar cane, tea,grapevines, hops, banana and natural rubber plants, as well asornamental plants (flowers, shrubs, deciduous trees and coniferous treessuch as conifers).

[0022] This is not intended to be a limiting list of plants. The activeingredient mixtures according to the invention are especiallyadvantageous for the following applications:

[0023] I+IIA: for cereals and vines;

[0024] I+IIB: for cereals, particularly wheat and barley, also forvines, vegetables and fruit;

[0025] I+IIC: for cereals;

[0026] I+IID: for vines;

[0027] I+IIE: for cereals;

[0028] I+IIF: for cereals, particularly wheat and barley, also for vinesand vegetables;

[0029] I+IIG: for treatment of seeds;

[0030] I+IIH: for vegetables and vines;

[0031] I+IIJ: for cereals and vines;

[0032] I+IIK: for cereals, particularly for wheat and barley.

[0033] The active ingredient mixtures of formulae I and II are normallyemployed in the form of compositions. The active ingredients of formulaeI and II may be applied to the area or plants to be treated eithersimultaneously or in succession on the same day, together with furtheroptional fillers, surfactants or other application-enhancing additiveswhich are customary in formulation techniques.

[0034] Appropriate fillers and additives may be solid or liquid, andcorrespond to the substances which are efficient in formulationtechniques, e.g. natural or regenerated mineral substances, solvents,dispersants, wetting agents, adhesion agents, thickeners, binding agentsor fertilisers.

[0035] A preferred method of applying an active ingredient mixturecontaining at least one of each of these active ingredients I and II isapplication to the parts of the plant above ground, especially the leafsystem (leaf application). The number of applications and applicationrate depend on the biological and climatic living conditions of theinstigator. However, the active ingredients may also reach the plantthrough the root system (systemic action) via the soil or the water,whereby the plant site is drenched with a liquid formulation (e.g. inrice cultivation) or the substances are incorporated into the soil insolid form, e.g. in the form of granules (soil application). Thecompounds of formulae I and II may also be applied to seed grain in aseed treatment (coating), whereby the tubers or grains are eitherimmersed in succession with a liquid formulation of each activeingredient, or are coated with an already combined, wet or dryformulation. In addition, in particular cases, further types of plantapplication are possible, e.g. the targeted treatment of buds orsyncarpy. Here, the compounds of the combination are used in unchangedform or preferably together with excipients which are usual informulation techniques, and they are processed in known manner e.g. intoemulsion concentrates, coatable pastes, directly sprayable or diluablesolutions, diluted emulsions, wettable powders, soluble powders, dusts,granules, or by encapsulation into, for example, polymeric substances.The application methods, such as spraying, misting, dusting, dispersing,coating or drenching, are selected according to the targeted aims andthe given conditions, in the same way as for selection of the type ofagent. Favourable application rates for the active ingredient mixtureare in general 50 g to 2 kg active substance per ha, especially 100 g to700 g active substance per ha, most preferably 75 g to 450 g activesubstance per ha. For the treatment of seeds, the application rates are0.5 g-600 g, preferably 5 g-80 g active substance per 100 kg seeds.

[0036] The formulations are produced in known manner, e.g. by intimatelymixing and/or grinding the active ingredients with diluting agents, e.g.solvents, solid fillers, and optionally surface-active compounds(surfactants).

[0037] The solvents in question may be: aromatic hydrocarbons,preferably fractions C₈ to C₁₂, such as xylene mixtures or substitutednaphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols, as well as the ethers and esters thereof, such as ethanol,ethylene glycol, ethylene glycol monomethyl ether or monoethyl ether,ketones such as cyclohexanone, strongly polar solvents such asN-methyl-2-pyrrolidone, dimethyl sulphoxide or dimethyl formamide, aswell as optionally epoxidated vegetable oils such as epoxidated coconutoil or soybean oil; or water.

[0038] The solid fillers, e.g. for dusting agents and dispersiblepowders, are normally natural mineral powder, such as calcitol, talcum,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, highly disperse silicic acid or highly disperse, absorbentpolymerisates may also be added. The granulated, adsorptive granulatefillers may be porous types such as pumice stone, brick fragments,sepiolite or bentonite, and non-sorptive fillers are e.g. calcitol orsand.

[0039] Furthermore, a number of pregranulated materials of inorganic ororganic nature may also be used, especially dolomite or pulverised plantresidues.

[0040] Depending on the type of active ingredients of formulae I and IIbe formulated, the surface-active compounds may be non-ionic, cationicand/or anionic surfactants with good emulsifying, dispersing and wettingproperties. By surfactants are also understood surfactant mixtures.

[0041] Especially advantageous, application-enhancing admixtures arealso natural or synthetic phospholipids from the series cephalins andlecithins, e.g. phosphatidylethanolamine, phosphatidylserine,phosphatidylglycerol, lysollecithin.

[0042] The agrochemical compositions normally contain 0.1 to 99%,especially 0.1 to 95% active ingredients of formulae I and II, 99.9 to1%, especially 99.9 to 5% of a solid or liquid additive and 0 to 25%,especially 0.1 to 25% of a surfactant.

[0043] While concentrated formulations are preferred as commercialproducts, the final user normally uses diluted formulations.

[0044] The following examples serve to illustrate the invention, whereby“active ingredient” indicates a mixture of compound I and compound II ina certain mixture ratio.

FORMULATION EXAMPLES

[0045] Wettable powder a) b) c) active ingredient [I:II = 1:3(a),1:2(b), 1:1(c)] 25% 50% 75% Na ligninsulphonate 5% 5% — Nalaurylsulphate 3% — 5% Na diisobutylnaphthalenesulphonate — 6% 10%octylphenol-polyethylene-glycol-ether — 2% — (7-8 mols ethylene oxide)highly disperse silicic acid 5% 10% 10% kaolin 62% 27% —

[0046] The active ingredient is mixed well with the additives and groundthoroughly in an appropriate mill. Spray powders are obtained, which canbe diluted with water to form suspensions of any desired concentration.Emulsifiable concentrate active ingredient (I:II = 1:6) 10% octylphenolpolyethylene glycol ether 3% (4-5 mols ethylene oxide) Cadodecyl-benzene-sulphonate 3% castor oil polyglycol ether (35 molsethylene oxide) 4% cyclohexanone 30% xylene mixture 50%

[0047] Emulsions of any desired dilution may be produced from thisconcentrate by diluting it with water, and they can be used in plantprotection. Coated granule active ingredient (I:II = 1:10) 8%polyethylene glycol (molecular weight 200) 3% kaolin 89%

[0048] The finely ground active ingredient is applied evenly to thekaolin which is moistened with polyethylene glycol, in a mixer. In thisway, dust-free coated granules are obtained.

BIOLOGICAL EXAMPLES

[0049] A synergistic effect is present if the activity of the activeingredient combination is greater than the sum of activities of theindividual components.

[0050] The activity E to be expected for a given active ingredientcombination obeys the so-called COLBY formula and may be calculated asfollows (COLBY, S. R. “Calculating synergistic and antagonisticresponses of herbicide combination”. Weeds, Vol.15, pages 20-22; 1967):

[0051] ppm=milligrams active ingredient (=ai) per liter spray mixture

[0052] X=% activity from active ingredient I during application of p ppmof active ingredient

[0053] Y=% activity from active ingredient II during application of qppm of active ingredient

[0054] The expected (additive) activity of active ingredients I+IIduring application of p+p ppm active ingredient is, according to Colby$E = {X + Y - \frac{X \cdot Y}{100}}$

[0055] If the activity actually observed (O) is greater than theexpected activity (E), then the combination is super-additive in itsactivity, i.e. there is a synergistic effect (SF=synergie factor).

[0056] B-1: Activity Against Puccinia recondita on Wheat

[0057] a) Residual Protective Activity

[0058] Wheat plants are sprayed until dripping wet, 6 days after sowing,with an aqueous spray mixture prepared from wettable powder of theactive ingredient mixture, and are infected 24 hours later with auredospore suspension of the fungus. After an incubation period of 48hours (conditions: 95 to 100% relative atmospheric humidity at 20° C.),the plants are placed in a greenhouse at 22° C. 12 days after infection,the fungal attack is evaluated.

[0059] b) Systemic Activity

[0060] 5 days after sowing, an aqueous spray mixture prepared fromwettable powder of the active ingredient mixture is poured onto wheatplants. Care is taken that the spray mixture does not come into contactwith the parts of the plants that are above ground. 48 hours later, theplants are infected with a uredospore suspension of the fungus. After anincubation period of 48 hours (conditions: 95 to 100% relativeatmospheric humidity at 20° C.), the plants are placed in a greenhouseat 22° C. 12 days after infection, the fungal attack is evaluated.

[0061] Active ingredient mixtures comprising components IIB and IIC inparticular demonstrate good synergistic activity.

Example B-2 Activity against Plasmopara viticola on Vines

[0062] Vine seedlings at the 4 to 5 leaf stage are sprayed untildripping wet with an aqueous spray mixture prepared from wettable powderof the active ingredient mixture, and are infected 24 hours later with asporangia suspension of the fungus. The fungal attack is evaluated 6days after infection, during which period the conditions of 95 to 100%relative atmospheric humidity and a temperature of 20° C. aremaintained.

[0063] Active ingredient mixtures comprising components IIB, IID and IIAin particular demonstrate good synergistic activity.

Example B-3 Activity against Erysiphe araminis on Barley

[0064] a) Residual Protective Activity

[0065] Barley plants of approximately 8 cm height are sprayed untildripping wet with an aqueous spray mixture prepared from wettable powderof the active ingredient mixture, and 3 to 4 hours later are dusted withconidia of the fungus. The infected plants are placed in a greenhouse at22° C. 12 days after infection, the fungal attack is evaluated.

[0066] b) Systemic Activity

[0067] An aqueous spray mixture prepared from wettable powder of theactive ingredient mixture is poured onto barley plants of approximately8 cm height. Care is taken that the spray mixture does not come intocontact with the parts of the plants that are above ground. 48 hourslater, the plants are dusted with conidia of the fungus. The infectedplants are placed in a greenhouse at 22° C. 12 days after infection, thefungal attack is evaluated. Active ingredient mixtures comprisingcomponents IIA, IID and IIE in particular demonstrate good synergisticactivity. TABLE 1 Active ingredient IIA = Quinoxyfen active activeingredient Test ingredient I IIA ratio % activity % activity SF No.mg/litre mg/litre I:II found O calculated E O/E 0 — — 0 (control) 1 0.1—  6 2 1.0 — 30 3 — 0.1  4 4 — 0.5  6 5 — 1.0  8 6 — 10.0 21 7 0.1 0.11:1  26 10 2.6 8 0.1 0.5 1:5  30 12 2.5 9 0.1 1.0 1:10 21 14 1.5 10  1.010.0 1:10 75 45 1.7

Example B4 Activity against Phytophthora infestans on Tomatoes

[0068] a) Curative Activity

[0069] Tomato plants of the variety “red gnome” are sprayed with azoospore suspension of the fungus after cultivating for three weeks, andincubated in a cabin at 18 to 20° C. and under saturated atmospherichumidity. The humidity is stopped after 24 hours. After drying off theplants, they are sprayed with a mixture which contains the activesubstances formulated as a wettable powder. When the spray coating hasdried on, the plants are again placed in the moist cabin for 4 days. Thenumber and size of typical leaf spots which have appeared after thisperiod are the criterion for evaluating the efficacy of the testedsubstances.

[0070] b) Preventive Systemic Activity

[0071] The active substances formulated as wettable powders are appliedto the surface of the soil of three week old tomato plants of thevariety “red gnome” which have been potted into single pots. Afterleaving for three days, the undersides of the leaves of the plants aresprayed with a zoospore suspension of Phytophthora infestans. They arethen kept for 5 days in a sprayed cabin at 18 to 20° C. and undersaturated atmospheric humidity. After this period, typical leaf spotsappear. The number and size thereof serve to evaluate the efficacy ofthe tested substances.

[0072] Active ingredient mixtures comprising components IIB and IIC inparticular demonstrate good synergistic activity.

Example B-5 Activity against Botrytis cinerea on Apple Fruits. ResidualProtective Action

[0073] Artificially damaged apples are treated by applying a spraymixture to the wound sites in drops. The treated fruits are theninoculated with a spore suspension of the fungus and incubated for oneweek at high atmospheric humidity and ca. 20° C. The fungicide action ofthe test substance is deduced from the number of wound sites that havestarted to rot. Active ingredient mixtures comprising components IIB andIIC in particular demonstrate good synergistic activity.

Example B-6 Activity against Fusarium nivale on Rye (Seed Treatment)

[0074] Rye of the variety “Tetrahell” which is naturally infected withFusarium nivale is dressed with the fungicide to be tested on a mixingroller, whereby the following concentrations are used: 20 or 6 ppm AS(based on the weight of the seeds).

[0075] The infected and treated rye is sown in the open in October witha seed drilling machine on plots of 3 m length and 6 seed rows. 3repeats per concentration. Up to evaluation of the attack, the testplantation is cultivated under normal field conditions (preferably in aregion with a closed snow cover during the winter months).

[0076] To evaluate the phytotoxicity, an appraisal is made of the seedemergence in the autumn and an appraisal is made in spring of the cropdensity/number of plants.

[0077] To determine the active ingredient activity, the percentage ofplants attacked by Fusarium is counted in spring, directly after thesnow has thawed. The active ingredient mixtures demonstrate goodsynergistic activity.

What is claimed is:
 1. A Microbicide composition for plants, containingat least two active ingredient components in an amount producingsynergistic activity, together with an appropriate filler, characterisedin that component I is2-[α-{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylicacid-methylester-O-methyloxime, and component II is a compound selectedfrom the group IIA) 5,7-dichloro-4-(4-fluorophenoxy)quinoline(“Quinoxyfen”); IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine(“Cyprodinil”); IIC)benzo(1,2,3)thiadiazole-7-carbothio-acid-S-methylester(“Acibenzolar-S-methyl”); IID)3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione(“Famoxadone”); IIE)8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine(“Spiroxamin”); IIF)4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile(“Fludioxonil”); IIG) 4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile(“Fenpiclonil”); IIH) 1-methyl-cyclohexanecarboxylicacid-(2,3-dichloro-4-hydroxy-phenyl)-amide (“Fenhexamid”); IIJ)2-{2-[6-(2-cyano-phenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxy-acrylicacid methyl ester (“Azoxystrobin”); IIK)Methoximino-(2-o-tolyloxymethyl-phenyl)-acetic acid methyl ester(“Kresoxim-methyl”); or repectively one of the salts or metal complexesof components I and II.
 2. A composition according to claim 1,characterised in that the weight ratio of I:II is 20:1 to 1:20.
 3. Acomposition according to claim 1, wherein component II is the compoundIIA) 5,7-dichloro-4-(4-fluorophenoxy)quinoline (“Quinoxyfen”).
 4. Amethod for the control and prevention of plant diseases, characterisedin that a site which has been attacked by fungi or is in danger of beingattacked by fungi is treated with component I and component II accordingto claim 1 in any order or simultaneously.